[go: up one dir, main page]

EP0541737A1 - N-PHENYL-CINNAMAMIDES, PROTECTIVE AGAINST THE HARMFUL EFFECTS OF ULTRA-VIOLET LIGHT. - Google Patents

N-PHENYL-CINNAMAMIDES, PROTECTIVE AGAINST THE HARMFUL EFFECTS OF ULTRA-VIOLET LIGHT.

Info

Publication number
EP0541737A1
EP0541737A1 EP92908925A EP92908925A EP0541737A1 EP 0541737 A1 EP0541737 A1 EP 0541737A1 EP 92908925 A EP92908925 A EP 92908925A EP 92908925 A EP92908925 A EP 92908925A EP 0541737 A1 EP0541737 A1 EP 0541737A1
Authority
EP
European Patent Office
Prior art keywords
phenyl
ultraviolet light
cinnamamides
function
foodstuffs
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92908925A
Other languages
German (de)
French (fr)
Other versions
EP0541737B1 (en
Inventor
Pierre Baudet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0541737A1 publication Critical patent/EP0541737A1/en
Application granted granted Critical
Publication of EP0541737B1 publication Critical patent/EP0541737B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/762—Organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
    • A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/16—Amides, e.g. hydroxamic acids
    • A61K31/165—Amides, e.g. hydroxamic acids having aromatic rings, e.g. colchicine, atenolol, progabide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A61K31/19—Carboxylic acids, e.g. valproic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
    • A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/38—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings

Definitions

  • N-phenyle-cinnamamides protectors against the harmful effects of ultraviolet light
  • Sunlight at the level of the Earth's crust, includes a portion of ultraviolet light whose spectrum ranges from 280 to 400 nm.
  • the shorter wavelength radiation is retained by the circumterreste ozone layer -in the upper atmosphere.
  • UV-C Ultraviolet light of short wavelengths at 280 nm is called UV-C, from 280 to 320 nm UV-B and from 320 to 400 nm UV-A.
  • UV-C The irradiation of a living organism by UV-C is lethal
  • UV-B irradiation is toxic, causing erythema and damage to the stratum corneum: UV-A irradiation causes browning of the skin by inducing, melanogenesis in melanocytes. from dopamine from tyrosine is transferred to the keratocytes. Browning makes the epidermis less sensitive to the toxic effect of UV-A which enter the dermis. However, it does not prevent UV-A from causing aging of the skin and the induction of skin carcinomas. The amount of UV-A reaching the earth's surface is approx. 1000 times greater than the amount of UV-B.
  • the human organism in particular the integuments (skin and hair) must be protected against the harmful effects of UV-A and UV-3 radiations from sunlight and this all the more so since the population is white and that it lives on continents with strong solar exposure or that it is temporarily exposed to strong solar irradiations.
  • filters or sunscreens containing inorganic or organic substances which reflect or absorb UV-A and UV-B light respectively.
  • the mineral substances are talc, zinc oxide and titanium oxide, they are called sunscreens. They are preferred for the aesthetics of translucent or milky solutions of organic molecules, sunscreens, in solution in creams, milks, lotions, these oils, gels, at a concentration of 0.5 to 10
  • the organic molecules are chosen according to their capacity for absorbing ultraviolet light UV-A and UV-B- and their harmlessness.
  • Cosmetic preparations almost always contain a mixture of UV-A and UV-B filters, in order to achieve the widest possible protection.
  • UV-A and UV-B sun filters are:
  • UV-A and UV-B light absorbability greater than
  • the present invention relates to organic substances which can be used as sun filters, sunscreens, protectors for foodstuffs and materials against alterations caused by ultraviolet light.
  • UV-A and UV-B light require a degree of unsaturation on the part of organic substances which increases from UV-B structures to UV-A structures.
  • the modulation of the absorbent properties also requires the presence of organic functions with an inductive effect (electron donor) on the unsaturated system, e.g. the alkoxy, hydroxy, amino, alkylamino functions, and in a favorable position by relation to these functions of groups of atoms (electron attractors), e.g. carboxy, carboalkoxy, carbamide, ketone, sulfonic, hitrile functions.
  • organic functions with an inductive effect e.g. the alkoxy, hydroxy, amino, alkylamino functions
  • Non-cyclic carbon unsaturated structures e.g. ethylene derivatives
  • undergo the cis-trans isomerism whose balance is often shifted by ultraviolet light towards the geometric isomer with the lowest absorbing power.
  • Unsaturation between two aromatic residues produced by two carbons is therefore not desirable.
  • a function comprising two polarizable centers between two aromatic residues is capable of creating a conjugation whose state excited by ultraviolet photons could be of energy relatively low compared to the ground state. This effect will cause, depending on the functions present, a hypsochromic or bathochromic or even auxochromic displacement of the spectral values, i.e. it will allow the choice of an appropriate structure for the preparation of a solar filter. wish.
  • the electron acceptor function B makes it possible to extend the polarization to the phenyl residue, the bathochromic effect increases (displacement towards or in UV-A); when the function A is less electron donor the hypsochromic effect is manifested (displacement towards or in UV-B).
  • N-phenyl-cinnamami ⁇ es we can make a sun filter with very high absorbing power of the ultraviolet light chosen. These properties give N-phenyl-cinnamamides, as sunglasses, protectors foodstuffs and materials against alterations caused by ultraviolet light, a quality of protection which is not known in sunscreens on the market (see Table I).
  • N-phenyl-cinnamamides The synthesis of N-phenyl-cinnamamides was carried out using appropriate cinnamic acid derivatives, the carboxy function of which has been transformed into acid chloride or acid anhydride or mixed anhydride or into activated esters or azide or into a derived from a carbodiimide reacting with the substituted or unsubstituted amino phenyl function, in an anhydrous solvent.
  • the products are crystallized from water and recrystallized from the solvent indicated in the description of N-phenyl-cinnamamides.
  • N-phenyl-cinnamamides of formula I used as sun filters and sunscreens in cosmetics and in medical applications, used as agents for protecting foodstuffs and materials against damage caused by ultraviolet light.
  • - R 1 is a hydrogen, an alkyl residue, saturated or not, branched or not, functionalized or not, an amino-primary function, a mono-alkyl-amino function, a dialkylamino function, an alkoxy function, a phenoxy function, a hydroxy function, a sulfo function, a suifamyl function, a ketone function, a halogen function,
  • R 2 , R 3 and R 4 are hydrogen, a saturated or non-saturated alkyl residue, branched or not, functionalized or not, a carboxylic carbonyl, a carboxylic ester, a carboxamide, an amide function with an amino acid, a peptide amide function, an amide function with an aromatic amine, an acylated amide function, an aliphatic ketone function, a ketone function linked to an aromatic residue, a ⁇ -ketone ketone function, a sulfo function, a sulfamyl function , a sulfone function, an amino-primary function, an amino-secondary function, an amino-tertiary function, a C 1 to C 6 alkoxy function, a hydroxy function, a nitrle function, a halogen function, a 2-benzimidazole residue , a remnant
  • R 2 , R 3 , R 4 can be present together or separately.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Zoology (AREA)
  • Polymers & Plastics (AREA)
  • Food Science & Technology (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Medical Uses (AREA)
  • Paints Or Removers (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

Les N-phenyl-cinnamamides peuvent être utilisés comme filtres solaires, écrans solaires UV-A, UV-B et UV-AB dans les préparations cosmétiques et médicales. Les N-phényl-cinnamamides peuvent être des agents de protection des denrées alimentaires et des matériaux contre les dégradations provoquées par la lumière ultra-violette.N-phenyl-cinnamamides can be used as sun filters, UV-A, UV-B and UV-AB sunscreens in cosmetic and medical preparations. N-phenyl-cinnamamides can be agents for protecting foodstuffs and materials against degradation caused by ultraviolet light.

Description

Les N-phénéyl-cinnamamides, protecteurs contre les effets nocifs de la lumière ultra-violette  N-phenyle-cinnamamides, protectors against the harmful effects of ultraviolet light

La lumière solaire, au niveau de l'écorce terrestre,comprend une partie de lumière ultra-violette dont le spectre s'étend de 280 à 400 nm.Les radiations de longueur d'onde plus courte sont retenues par la couche d'ozone circumterreste-dans la haute atmosphère. Sunlight, at the level of the Earth's crust, includes a portion of ultraviolet light whose spectrum ranges from 280 to 400 nm. The shorter wavelength radiation is retained by the circumterreste ozone layer -in the upper atmosphere.

La lumière ultra-violette des courtes longueurs d'ondes à 280 nm est appelée UV-C,de 280 à 320 nm UV-B et de 320 à 400 nm UV-A.  Ultraviolet light of short wavelengths at 280 nm is called UV-C, from 280 to 320 nm UV-B and from 320 to 400 nm UV-A.

L'irradiation d'un organisme vivant par les UV-C est léthale;  The irradiation of a living organism by UV-C is lethal;

l'irradiation par les UV-B est toxique, provoquant de l'érythème et des lésions du stratum corneum: l'irradiation par les UV-A provogue le brunissement de la peau en induisant, la mélanogenèse dans les mélanocytes.La mélanine formée à partir de la dopamine provenant de la tyrosine est transférée dans le kératocytes.Ie brunissement rend l'épiderme moins sensible à l'effet toxique des UV-A gui pénétrent dans le derme. Il n'empêche cependant pas les UV-A de provoquer le vieillissement de la peau et l'induction de carcinomes cutanés. La quantité de UV-A parvenant sur la surface terrestre est env.1000 fois plus importante que la quantité de UV-B.  UV-B irradiation is toxic, causing erythema and damage to the stratum corneum: UV-A irradiation causes browning of the skin by inducing, melanogenesis in melanocytes. from dopamine from tyrosine is transferred to the keratocytes. Browning makes the epidermis less sensitive to the toxic effect of UV-A which enter the dermis. However, it does not prevent UV-A from causing aging of the skin and the induction of skin carcinomas. The amount of UV-A reaching the earth's surface is approx. 1000 times greater than the amount of UV-B.

L'organisme humain,en particulier les téguments (peau et cheveux) doit être protégé contre les effets nifastes des radiations UV-A et UV-3 de la lumière solaire et cela d'autant plus que la population est de race blanche et qu'elle vit sur des continents à forte exposition solaire ou qu'elle s'expose momentanément à de fortes irradiations solaires.  The human organism, in particular the integuments (skin and hair) must be protected against the harmful effects of UV-A and UV-3 radiations from sunlight and this all the more so since the population is white and that it lives on continents with strong solar exposure or that it is temporarily exposed to strong solar irradiations.

Pour réaliser cette protection on a créé des produits cosmétiques, appelés filtres ou écrans solaires, contenant des substances inorganiques ou organiques qui réfléchissent ou absorbent respectivement la lumière UV-A et UV-B. Les substances minérales sont le talc, l'oxyde de zinc et l'oxyde de titane,on les appelle des écrans solaires. On leurs préfère pour l'esthétique des solutions translucides ou laiteuses de molécules organiques, les filtres solaires, en solution dans des crèmes,des laits,des lotions, ces huiles,des gels,à raison d'une concentration de 0,5 à 10 %.Les molécules organiques sont choisies en fonction de leur pouvoir dâbsorption de la lumière ultraviolette UV-A et UV-B- et de leur inocuité.  To achieve this protection, cosmetic products have been created, called filters or sunscreens, containing inorganic or organic substances which reflect or absorb UV-A and UV-B light respectively. The mineral substances are talc, zinc oxide and titanium oxide, they are called sunscreens. They are preferred for the aesthetics of translucent or milky solutions of organic molecules, sunscreens, in solution in creams, milks, lotions, these oils, gels, at a concentration of 0.5 to 10 The organic molecules are chosen according to their capacity for absorbing ultraviolet light UV-A and UV-B- and their harmlessness.

Dans le tableau I nous présentons les principaux filtres solaires commercialisés,en indiquant leur longueur d'onde maximum de leur spectre d'absorption UV A et UV-B ( λ max. ) et l'intensité de leur pouvoir d'absorption des UV-A et UV-B,exprimé en coefficient d'extinction moléculaire ( ε max.), leur appartenance à la classe des UV. Tableau I filtres λ max ε max UV In Table I we present the main sunscreens sold, indicating their maximum wavelength of their UV A and UV-B absorption spectrum (λ max.) And the intensity of their UV-absorbing power. A and UV-B, expressed as molecular extinction coefficient (ε max.), Their belonging to the UV class. Table I filters λ max ε max UV

(nm)  (nm)

1 ) acide para-amino-benzoique 283 15300 B 1) para-amino-benzoic acid 283 15300 B

2 ) para-diméthylamino-benzoate d 'octyle 311 27300 B2) octyl para-dimethylamino benzoate 311 27 300 B

3 ) 4-méthoxy-2-hydroxy-benzophénone 288 14000 B 3) 4-methoxy-2-hydroxy-benzophenone 288 14000 B

325 9400 A 325 9400 A

4 ) 4-méthoxy-2-hydαxy-3-sulfo-benzophénonee 286 13400 B 4) 4-methoxy-2-hydroxy-3-sulfo-benzophenone 286 13 400 B

325 8400 A 325 8400 A

5 ) 2 , 2 ' -dihydroxy-4-méthoxy-benzophénone 284 13270 B 5) 2, 2 '-dihydroxy-4-methoxy-benzophenone 284 13270 B

327 10440 A 327 10440 A

6 ) 4-mêthoxy-cinnamate de 2-éthyl-héxyle 311 23300 B6) 2-ethyl-hexyl 4-methoxy-cinnamate 311 23 300 B

7 ) 4 -mé thoxy-4 ' -n-butyl-dibenzoyl-méthanes 358 34720 A solvant: éthanol 7) 4 -me thoxy-4 '-n-butyl-dibenzoyl-methanes 358 34720 Solvent: ethanol

Les préparations cosmétiques contiennent presque toujours un mélange de filtres UV-A et UV-B,afin de réaliser la plus large protection possible. Cosmetic preparations almost always contain a mixture of UV-A and UV-B filters, in order to achieve the widest possible protection.

Les qualités idéales des filtres solairesUV-A et UV-B sont les suivantes:  The ideal qualities of UV-A and UV-B sun filters are:

1) une absorbabilité de la lumière UV-A et UV-B supérieure à  1) UV-A and UV-B light absorbability greater than

ε max.20000,  ε max. 20000,

2) une bonne photostabilité,  2) good photostability,

3) une bonne stabilité chimique,  3) good chemical stability,

4) une bonne fixation au stratum corneum,  4) good fixation to the stratum corneum,

5) une bonne incorporation à la composition cosmétique,  5) good incorporation into the cosmetic composition,

6) une bonne inocuité,  6) good safety,

7) ne pas tacher.  7) do not stain.

La présente invention concerne des substances organiques utilisables en qualité de filtre solaires,d'écrans solaires,de protecteurs des denrées alimentaires et des matériaux contre les altérations provoquées par la lumière ultra-violette.  The present invention relates to organic substances which can be used as sun filters, sunscreens, protectors for foodstuffs and materials against alterations caused by ultraviolet light.

La structure de ces substances organiques a été choisie en fonctionThe structure of these organic substances was chosen according to

1) de leur grand pouvoir absorbant la lumière UV-A et UV-B 1) of their great capacity to absorb UV-A and UV-B light

(εmax suprérieur à 20000),  (εmax greater than 20000),

2) de leur photostabilité,  2) their photostability,

3) de leur parentee à des substances déjà utilisées comme filtres solaires,dont on a reconnu à l'échelle mondiale, leur inocuité sanitaire, 3) their parentage to substances already used as filters sunscreen, whose health safety has been recognized worldwide,

4) leur re'sistivité en milieu aqueux,  4) their resistivity in an aqueous medium,

5) leur appartenance à une même famille de composés dont de faible variation permet de moduler leurs propriétés UV-A et UV-B.  5) their belonging to the same family of compounds, of which a small variation makes it possible to modulate their UV-A and UV-B properties.

Une bonne absorbabilité des lumières UV-A et UV-B requiert de la part des substances organiques un degré d1 insaturation qui augmente en passant des structuresUV-B aux structures UV-A.  Good absorbability of UV-A and UV-B light requires a degree of unsaturation on the part of organic substances which increases from UV-B structures to UV-A structures.

La modulation des propriété absorbantes,exprimées en ε max, requiert aussi la présence de fonctions organiques à effet inductif (donneur d'électrons)sur le système insaturé,par ex.les fonctions alkoxy,hydroxy,amino,alkylamino, et en position favorable par rapport à ces fonctions des groupements d'atomes (attireurs d'électrons), par ex. les fonctions carboxy,carboalkoxy, carbamides, cétonique,sulfonique,hitrile. The modulation of the absorbent properties, expressed in ε max, also requires the presence of organic functions with an inductive effect (electron donor) on the unsaturated system, e.g. the alkoxy, hydroxy, amino, alkylamino functions, and in a favorable position by relation to these functions of groups of atoms (electron attractors), e.g. carboxy, carboalkoxy, carbamide, ketone, sulfonic, hitrile functions.

Les structures insaturée au carbone,non cyclique, par ex. les dérivés de l'éthylène, subissent l'isomérie cis-trans,dont souvent l'équilibre est déplacé par la lumière ultra-violette vers l'isomère géométrique au pouvoir absorbant le plus bas. Une insaturation entre deux restes aromatiques réalisée par deux carbones n'est donc pas souhaitable.Par contre, une fonction comprenant deux centres polarisables entre deux restes aromatiques est susceptible de créer une conjugaison dont l'état excité par les photons ultraviolets pourrait être d'énergie relativement peu élevée par rapport à l'état fondamental.Cet effet provoquera selon les fonctions présentes un déplacement hypsochromique ou bathochromique voire auxochromique des valeurs spectrales c-à-d il permettra le choix d'une structure appropriée pour la préparation d'un filtre solaire souhaité.  Non-cyclic carbon unsaturated structures, e.g. ethylene derivatives, undergo the cis-trans isomerism, whose balance is often shifted by ultraviolet light towards the geometric isomer with the lowest absorbing power. Unsaturation between two aromatic residues produced by two carbons is therefore not desirable. On the other hand, a function comprising two polarizable centers between two aromatic residues is capable of creating a conjugation whose state excited by ultraviolet photons could be of energy relatively low compared to the ground state. This effect will cause, depending on the functions present, a hypsochromic or bathochromic or even auxochromic displacement of the spectral values, i.e. it will allow the choice of an appropriate structure for the preparation of a solar filter. wish.

Nous avons choisi pour la fonction intermédiaire,polarisable,entre une reste cinnamyle et un reste phényle,la fonction-CONH-, réalisant les N-phényl-cinnamamides.Leur pouvoir d'absorption de la lumière entre 280 et 350 nm(UV-B et UV-A) est très élevé.La position de leur λ max.peutêtre choisie en vertu des fonctions donneur et accepteur d'électrons placées séparément sur le reste cinnamyl d'un côté et sur le reste phényl de l'autre. Pour la raison de la meilleure transmission de cet effet à travers toute la molécule,nous préférons les positions para et ortho par rapport à la place de la fonction intermêdiaire-CONH- Les quatre structures générales des N-phényl-cinnamamides de l'invention sont représentées dans le tableau II, We have chosen for the intermediate, polarizable function, between a cinnamyl residue and a phenyl residue, the-CONH- function, producing the N-phenyl-cinnamamides. Their power of absorbing light between 280 and 350 nm (UV-B and UV-A) is very high. The position of their max λ can be chosen by virtue of the electron donor and acceptor functions placed separately on the cinnamyl residue on one side and on the phenyl residue on the other. For the reason of the better transmission of this effect across the whole molecule, we prefer the para and ortho positions with respect to the place of the intermediate function-CONH- The four general structures of the N-phenyl-cinnamamides of the invention are shown in Table II,

Lorsque à partir de la fonction donneur d'électrons A, la fonction B accepteur d'électrons permet d'étendre la polarisation au reste phényle, l'effet bathochromique augmente(déplacement vers ou dans les UV-A);lorsque la fonction A est moins donneur d'électrons l'effet hypsochromique se manifeste( déplacement vers ou dans les UV-B).  When, starting from the electron donor function A, the electron acceptor function B makes it possible to extend the polarization to the phenyl residue, the bathochromic effect increases (displacement towards or in UV-A); when the function A is less electron donor the hypsochromic effect is manifested (displacement towards or in UV-B).

Ainsi,dans la même famille de subtances, les N-phényl-cinnamamiάes, on peut confectionner un filtre solaire à très fort pouvoir absorbant de la lumière ultra-violette choisie.Ces propriétés confèrent aux N-phényl-cinnamamides,comme fitres solaires,protecteurs des denrées alimentaires et des matériaux contre les altérations provoquées par la lumière ultra-violette,une qualité de protection que l'on ne connaît pas chez les filtres solaires commercialisés (voir le tableau I).  Thus, in the same family of substances, N-phenyl-cinnamamiάes, we can make a sun filter with very high absorbing power of the ultraviolet light chosen. These properties give N-phenyl-cinnamamides, as sunglasses, protectors foodstuffs and materials against alterations caused by ultraviolet light, a quality of protection which is not known in sunscreens on the market (see Table I).

Les exemples:  The examples:

La synthèse des N-phényl-cinnamamides a été effectuée à partir des dérivé appropriés de l'acide cinnamique dont la fonction carboxy a été transformée en chlorure d'acide ou anhydride d'acide ou anhydride mixte ou en esters activés ou azide ou en un dérivé d'une carbodiimide réagissant avec la fonction amino phényl substitué ou non, dans un solvant anhydre.Les produits sont cristallisés dans l'eau et recristallisés.dans le solvant indiqué dans la description des N-phényl-cinnamamides.  The synthesis of N-phenyl-cinnamamides was carried out using appropriate cinnamic acid derivatives, the carboxy function of which has been transformed into acid chloride or acid anhydride or mixed anhydride or into activated esters or azide or into a derived from a carbodiimide reacting with the substituted or unsubstituted amino phenyl function, in an anhydrous solvent. The products are crystallized from water and recrystallized from the solvent indicated in the description of N-phenyl-cinnamamides.

Les analyses ont portés sur la composition C,H,N,S;les points de fusion sont déterminés avec l'appareil de Kofler(Reichert);les spectres UV ont été établis avec le spectrometre Cary 2300;les spectres IR ont été obtenus avec le spectrometre 735 B de Perkin-Elmer. Exemple 1 N- ( 4 -carbéthoxy-phényl ) -4 -méthoxy-cinnamamide The analyzes focused on the composition C, H, N, S; the melting points are determined with the Kofler apparatus (Reichert); the UV spectra were established with the Cary 2300 spectrometer; the IR spectra were obtained with the Perkin-Elmer spectrometer 735 B. Example 1 N- (4 -carbethoxy-phenyl) -4 -methoxy-cinnamamide

C19H19NO4 ( 325 ) , éthanol , F . 150-152º , C 19 H 19 NO 4 (325), ethanol, F. 150-152º,

UV:nm 380 370 360 350 340 330 320 310 300  UV: nm 380 370 360 350 340 330 320 310 300

450 1810 8170 20360 34920 45570 46230 39580 33050 450 1810 8170 20360 34920 45570 46230 39580 33050

290 280 270 290 280 270

26030 19690 14200 λ max.= 325 nm ε max. =47230  26,030 19,690 14,200 max. = 325 nm max. = 47230

IR(nujol): 3280,1705,1680,1660,1620,1590,1510,1410,1340,132θ,1275, IR (nujol): 3280,1705,1680,1660,1620,1590,1510,1410,1340,132θ, 1275,

1250, 1175, 1105 (doublet), 1030, 980, 855, 840, 780 cm-1 1250, 1175, 1105 (doublet), 1030, 980, 855, 840, 780 cm -1

Exemple 2 N-(2-carbéthoxy-phényl)-4-méthoxy-cinnamamide Example 2 N- (2-carbethoxy-phenyl) -4-methoxy-cinnamamide

C19H19NO4(325), éthanol, F.125-127°, C 19 H 19 NO 4 (325), ethanol, F. 125-127 °,

UV:nm 380 370 360 350 340 330 320 310 300 UV: nm 380 370 360 350 340 330 320 310 300

610 2000 8590 17610 27830 32310 29870 27720 25480  610 2,000 8,590 17,610 27,830 32,310 29,870 27,720 25,480

290 280 275 290 280 275

21580 17200 15310 λ max.= 329.3 nm ε max. =32450  21580 17200 15310 λ max. = 329.3 nm ε max. = 32450

IR(nujol): 3180-3300(large, faible), 1675, 1630, 1600-1590,1530-1500  IR (nujol): 3180-3300 (wide, weak), 1675, 1630, 1600-1590, 1530-1500

(triplet), 1335, 1310-1290,1255, 1170, 1090, 1060-1030,1000, 980,880,855-830,810,765 cm-1. (triplet), 1335, 1310-1290,1255, 1170, 1090, 1060-1030,1000, 980,880,855-830,810,765 cm -1 .

Exemple 3 N-(4-carboxy-phényl)-4-méthoxy-cinnamamide Example 3 N- (4-carboxy-phenyl) -4-methoxy-cinnamamide

C17H15NO4(297),eau,F.recrist.dés 225º,F. 275-277º, C 17 H 15 NO 4 (297), water, F.recrist.dés 225º F. 275-277º,

UV:nm 380 370 360 350 340 330 320 310 300 UV: nm 380 370 360 350 340 330 320 310 300

570 2430 7800 18260 31720 42890 45170 39100 32220  570 2,430 7,800 18,260 31,720 42,890 45,170 39,100 32,220

290 280 270 290 280 270

24800 17850 12480 λ max.= 323,4 nm ε max.= 45560 IB(nujol) : 3260,1670(ép.),1650,1590(doublet),1520(ép.),1500,1410, 1320,1280(doublet),1245,1155,1030-1000(triplet),970, 930(doublet),875,860(ép.),835,78= cm-1. 24,800 17,850 12,480 max λ = 323.4 nm max ε = 45,560 IB (nujol): 3260.1670 (thick), 1650.1590 (doublet), 1520 (thick), 1500.1410, 1320.1280 (doublet), 1245.1155.1030-1000 (triplet), 970, 930 (doublet), 875.860 (th.), 835.78 = cm -1 .

Exemple 4 N-(4-sulfo-Dhényl)-4-méthoxy-cinnamamide(sel de triéthylamine) Example 4 N- (4-sulfo-Dhenyl) -4-methoxy-cinnamamide (triethylamine salt)

C22H30N2O5S (434),acétonitrile( 2º ) ,F.148-150º, C 22 H 30 N 2 O 5 S (434), acetonitrile (2º), F.148-150º,

UV:nm 380 370 360 350 340 330 320 310 300  UV: nm 380 370 360 350 340 330 320 310 300

540 132o 4820 132402601038620 43310 39170 33320  540 132o 4820 132402601038620 43310 39170 33320

290 280 270 290 280 270

26250 19730 14130 λ max.=320 nm εmax.= 43310  26 250 19730 14130 λ max. = 320 nm εmax. = 43310

IR(nujol): 3200,2660-2680(doublet),1665,1620(ép.),1585(doublet), IR (nujol): 3200.2660-2680 (doublet), 1665.1620 (thick), 1585 (doublet),

1530,1510,1340,1295,1230(triplet),1160(doublet),1030, 1005 (doublet),850(triplet),730,700 cm-1. 1530,1510,1340,1295,1230 (triplet), 1160 (doublet), 1030, 1005 (doublet), 850 (triplet), 730,700 cm -1 .

Exemple 5 N-(4-benzoyl-carboxamido-phényl)-4-méthoxy-cinnamamide  Example 5 N- (4-benzoyl-carboxamido-phenyl) -4-methoxy-cinnamamide

C24H20N2O4(400),éthanol, F recrist. dés 245°,F.272-273, C 24 H 20 N 2 O 4 (400), ethanol, F recryst. from 245 °, F.272-273,

UV:nm 380 370 360 350 340 330 320 310 300 UV: nm 380 370 360 350 340 330 320 310 300

850 3300 11630 26030 42760 5503056110 47400 38500  850 3300 11630 26030 42760 5503056110 47400 38500

290 280 270 290 280 270

293802130014920 λmax.= 324 nm ε max.= 57160 293802130014920 λmax. = 324 nm ε max. = 57160

Revendications Claims

1.-Ies N-phényl-cinnamamides de la formule I,utilisés en qualité de filtres solaires et d'écrans solaires en cόnsmétique et en applications médicales,utilisés en qualité d'agents de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette. 1.-The N-phenyl-cinnamamides of formula I, used as sun filters and sunscreens in cosmetics and in medical applications, used as agents for protecting foodstuffs and materials against damage caused by ultraviolet light.

dans laquelle- R1 est un hydrogène, une reste alkyl saturé ou non, ramifié ou non,fonctionnalisé ou non,une fonction amino-primaire,une fonction mono-alkyl-amino,une fonction dialkylamino,une fonction alkoxy, une fonction phénoxy, une fonction hydroxy, une fonction sulfo,une fonction suifamyl,une fonction cétonique,une fonction halogène, in which - R 1 is a hydrogen, an alkyl residue, saturated or not, branched or not, functionalized or not, an amino-primary function, a mono-alkyl-amino function, a dialkylamino function, an alkoxy function, a phenoxy function, a hydroxy function, a sulfo function, a suifamyl function, a ketone function, a halogen function,

dans laquelle R2,R3 et R4 sont un hydrogène,un reste alkyl saturé on non, ramifié ou non, fonctionnalise ou non,un carbonyle carboxylique,un ester carboxylique,une carboxamide,une fonction amide avec un acide-aminé,une fonction amide peptidique,une fonction amide avec une aminé aromatique,une fonction amide acylés,une fonction cétonique aliphatique,une fonction cétonique lié à un reste aromatique,une fonction cétonique β di-cétonique,une fonction sulfo,une fonction sulfamyl,une fonction sulfoxyde,une fonction sulfone,une fonction amino-primaire, une fonction amino-secondaire,une fonction amino-tertiaire, une fonction alkoxy en C1 à C6,une fonction hydroxy,une fonction nitrle,une fonction halogène,un reste 2-benzimidazole,un restein which R 2 , R 3 and R 4 are hydrogen, a saturated or non-saturated alkyl residue, branched or not, functionalized or not, a carboxylic carbonyl, a carboxylic ester, a carboxamide, an amide function with an amino acid, a peptide amide function, an amide function with an aromatic amine, an acylated amide function, an aliphatic ketone function, a ketone function linked to an aromatic residue, a β-ketone ketone function, a sulfo function, a sulfamyl function , a sulfone function, an amino-primary function, an amino-secondary function, an amino-tertiary function, a C 1 to C 6 alkoxy function, a hydroxy function, a nitrle function, a halogen function, a 2-benzimidazole residue , a remnant

2-benzothiazole, 2-benzothiazole,

R2,R3, R4 peuvent être présents ensemble ou séparément. R 2 , R 3 , R 4 can be present together or separately.

Les autres positions aromatiques peuvent être également substituées par des fonctions ou restes qui seraient utiles à l'usage proposé.  The other aromatic positions can also be substituted by functions or residues which would be useful for the proposed use.

Claims

2 . - Une N-phényl-cinnamamide de la formule II, caractérisée par ses propriétés de filtre solaire UV-A et UV-B,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette, 2. - An N-phenyl-cinnamamide of formula II, characterized by its properties of UV-A and UV-B sunscreen, of protection of foodstuffs and materials against damage caused by ultraviolet light, 3.- Une N-phényl-cinnamamide de la formule III,caractérisée par ses propriétés de filtre solaire UV-A et UV-B,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette, 3.- An N-phenyl-cinnamamide of formula III, characterized by its properties of UV-A and UV-B sunscreen, of protection of foodstuffs and materials against damage caused by ultraviolet light, 4.- Une N-phényl-cinnamamide de la formule IV, caractérisée par ses propriétés de filtre solaire UV,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette, 4.- An N-phenyl-cinnamamide of formula IV, characterized by its properties of UV solar filter, of protection of foodstuffs and materials against damage caused by ultraviolet light, 5.- Une N-phényl-cinnamamide de la formule V,caractérisée par ses propriétés de filtre solaire UV,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette. 5.- An N-phenyl-cinnamamide of formula V, characterized by its properties of UV sun filter, protection of foodstuffs and materials against damage caused by ultraviolet light. 6.- Une N-phényl-cinamamide de la formule VI,caractérisée par ses propriétés de filtre solaire UV,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par lalumière ultra-violette, 6.- An N-phenyl-cinamamide of formula VI, characterized by its properties of UV solar filter, of protection of foodstuffs and materials against damage caused by ultra-violet light, 7.- Une N-phényl-cinnamamide de la formule VII, caractérisée par ses propriétés de. filtresolaire UV,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette, 7.- An N-phenyl-cinnamamide of formula VII, characterized by its properties of. UV polar filters, for protecting foodstuffs and materials against damage caused by ultraviolet light, 8.- Une N-phényl-cinnamamide de la formule VIII,caractérisée par ses propriétés de filtre solaire,de protection des denrées alimentaires et des matériaux contre les dommages provoqués par la lumière ultra-violette.  8.- An N-phenyl-cinnamamide of formula VIII, characterized by its properties of sun filter, protection of foodstuffs and materials against damage caused by ultraviolet light. 9.- Usage selon les revendications de 1 à 8 des N-phényl-cinnamamides en qualité de filtres solaires UV-A,UV-B,UV-AB,d'écrans solaires, pour des applications dans toutes les formulations cosmétiques et toutes les formulations pour des applications médicales,  9. Use according to claims 1 to 8 of N-phenyl-cinnamamides as sun filters UV-A, UV-B, UV-AB, sunscreens, for applications in all cosmetic formulations and all formulations for medical applications, 10.- Usage selonles revendications de 1 à 8 des N-phényl-cinnamamides en qualité d'agents de protection des denrées alimentairescontre les dommages provoqués par la lumière ultra-violette. 10. Use according to claims 1 to 8 of N-phenyl-cinnamamides as agents for protecting foodstuffs against damage caused by ultraviolet light. 11.-Usage selon les revendications 1 à 8 des N-phényl-cinnamamides en qualité d'adents de protection des matériaux contre les dommages provoqués par la lumière ultra-violette. 11. Use according to claims 1 to 8 of N-phenyl-cinnamamides as protection agents for materials against damage caused by ultraviolet light.
EP92908925A 1991-05-02 1992-05-01 N-phenyl-cinnamamides providing protection from the harmful effects of ultraviolet light Expired - Lifetime EP0541737B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1305/91 1991-05-02
CH130591 1991-05-02
PCT/CH1992/000088 WO1992019223A1 (en) 1991-05-02 1992-05-01 N-phenyl-cinnamamides providing protection from the harmful effects of ultraviolet light

Publications (2)

Publication Number Publication Date
EP0541737A1 true EP0541737A1 (en) 1993-05-19
EP0541737B1 EP0541737B1 (en) 1997-04-09

Family

ID=4207338

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92908925A Expired - Lifetime EP0541737B1 (en) 1991-05-02 1992-05-01 N-phenyl-cinnamamides providing protection from the harmful effects of ultraviolet light

Country Status (6)

Country Link
EP (1) EP0541737B1 (en)
JP (1) JPH06501490A (en)
AT (1) ATE151408T1 (en)
AU (1) AU1664892A (en)
DE (1) DE69218888D1 (en)
WO (1) WO1992019223A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4437502A1 (en) * 1993-12-02 1995-06-08 Basf Ag Conjugates of hirudin with lipophilic cpds.
US6080880A (en) * 1997-11-28 2000-06-27 Societe L'oreal S.A. Silicone-substituted cinnamamide/malonamide/malonate compounds and photoprotective compositions comprised thereof
KR100492809B1 (en) * 2001-11-23 2005-06-03 한국화학연구원 4-hydroxycinnamamide derivatives as antioxidants, process for preparing thereof and pharmaceutical compositions containing them
AU2002344453B2 (en) * 2002-11-05 2009-04-09 Lead Chemical Co.,Ltd. Compound protecting against ultraviolet
CN104304244B (en) * 2014-09-11 2016-08-24 广西田园生化股份有限公司 A kind of ultraviolet-resistant absorbent in pesticidal preparations
WO2024200549A1 (en) * 2023-03-28 2024-10-03 Roka Furadada, S.L. Dibenzoylmethane compounds as photochemical precursors of ultraviolet absorbers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337270A (en) * 1980-05-21 1982-06-29 Hisamitsu Pharmaceutical Co., Inc. Novel anthranilic acid derivatives
DE3219643A1 (en) * 1982-05-25 1983-12-01 Haarmann & Reimer Gmbh IF ANY, IN THE FORM OF A SALT, PRESENT CINNAMIC ACID (P-SULFO-PHENYLAMIDE), A METHOD FOR THE PRODUCTION THEREOF AND ITS USE IN LIGHT PROTECTION AGENTS
US4536346A (en) * 1983-05-06 1985-08-20 American Cyanamid Company Aralkanamidophenyl compounds
US4883653A (en) * 1984-06-25 1989-11-28 Olin Corporation Aryl N,N-bis cinnamamide compounds and their use as ultraviolet light stabilizers
FR2594332B1 (en) * 1986-02-14 1988-12-16 Jung Louis DERIVATIVES OF AMINO-BENZOIC ACIDS, HYDROXY-BENZOIC ACIDS, CINNAMIC ACIDS, UROCANIC ACID AND BENZIMIDAZOLE WITH OR WITHOUT A GROUP OF AMINO ACID ABSORBING UVB AND / OR UVA AND FOR AVOIDING PHOTODERMATOSES, IN MAN, CONSECUTIVE TO THE ADMINISTRATION OF MEDICINES, TO THE USE OF COSMETIC PERFUMES OR PERFUMES

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9219223A1 *

Also Published As

Publication number Publication date
EP0541737B1 (en) 1997-04-09
WO1992019223A1 (en) 1992-11-12
AU1664892A (en) 1992-12-21
JPH06501490A (en) 1994-02-17
DE69218888D1 (en) 1997-05-15
ATE151408T1 (en) 1997-04-15

Similar Documents

Publication Publication Date Title
BE1000623A3 (en) PHOTOSTABLE COSMETIC COMPOSITION CONTAINING A UV-A FILTER AND A UV-B FILTER, ITS USE FOR PROTECTING THE SKIN AGAINST UV RAYS AND A METHOD OF STABILIZING THE UV-A FILTER BY THE UV-B FILTER.
EP0507691B1 (en) S-triazine derivatives substituted with benzalmalonates, process for their preparation, filtering cosmetic compositions containing them and their use as UV-protectors for skin and hair
CA2076003C (en) Photostable cosmetic filtering composition containing a uv-a filter and an alkyl beta,beta-diphenylacrylate or o-cyano-beta,beta- diphenylacrylate
EP0507692B1 (en) S-Triazine derivatives substituted with benzylenecampher, process for their preparation, filtering cosmetic compositions containing them and their use as UV protectors for skin and hair
EP0717982B1 (en) Process for photostabilizing of dibenzoylmethan derivatives of sunscreen agent, the photostable cosmetic sunscreen compositions and their use
EP0944624B1 (en) Insoluble s-triazine derivatives and their use as uv filters
FR2799119A1 (en) Improving UV-radiation stability of photosensitive skin-protecting solar filters used in cosmetics involves use of photo-stabilizing material including at least one silicon alkoxide and surfactant
FR2744721A1 (en) NOVEL INSOLUBLE DERIVATIVES OF S-TRIAZINE, PROCESS FOR THEIR PREPARATION, COMPOSITIONS CONTAINING SAME, AND USES THEREOF
EP0542941B1 (en) N-phenyl-benzamides providing protection from the harmful effects of ultraviolet light
FR2620618A1 (en) PHOTOSTABLE FILTERING COSMETIC COMPOSITION CONTAINING BIXINE ASSOCIATED WITH LIPOSOLUBLE UV FILTER AND USE THEREOF FOR PROTECTION OF HUMAN EPIDERM FROM ULTRAVIOLET RADIATION
WO2023281224A1 (en) Anti-sun cosmetic composition containing mycosporine-like amino acids
FR2636530A1 (en) EMULSION PHOTOSTABLE FILTERING COSMETIC COMPOSITION CONTAINING A WATER SOLUBLE WIDE-BAND WATER FILTER AND AT LEAST ONE UV-A LIPOSOLUBLE FILTER AND USE THEREOF FOR PROTECTING SKIN FROM ULTRAVIOLET RADIATION
LU84789A1 (en) SUNSCREEN COMPOSITIONS
EP0970961B1 (en) Photostabilisation of dibenzoylmethane-based sunscreens, cosmetic sunscreen compositions thus obtained, and their use
EP0541737A1 (en) N-PHENYL-CINNAMAMIDES, PROTECTIVE AGAINST THE HARMFUL EFFECTS OF ULTRA-VIOLET LIGHT.
FR2782516A1 (en) METHOD FOR PHOTOSTABILIZING SUN FILTERS DERIVED FROM DIBENZOYLMETHANE, PHOTOSTABILIZED FILTERING COSMETIC COMPOSITIONS OBTAINED THUS AND THEIR USE
EP3103436B1 (en) Compounds derived from 3-(alkylthio)propenoic acid, and the use thereof in cosmetics
CA2564493C (en) Monomer 5,6-diphenyl-1,2,4-triazinic derivatives and the use thereof
FR2730927A1 (en) USE OF DIHYDROXYACETONE
FR2749510A1 (en) Sunscreen composition containing betulinic acid
EP0376652A2 (en) Ultraviolet radiation absorbing compositions of 1-cyclohexenylacetonitrile deriatives of aldehydes
EP2039341B1 (en) Cosmetic compositions comprising thiazolidine derivatives for use against the consequences of oxidising stress of the skin
FR2801211A1 (en) A cosmetic composition for artificial suntanning contains an active auto-tanning compound and a naphthalenic compound with an excited triplet energy level of specific amount
JPH0665037A (en) Ultraviolet absorber

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE DK ES FR GB GR IT LU NL SE

17P Request for examination filed

Effective date: 19930511

17Q First examination report despatched

Effective date: 19941205

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE DK ES FR GB GR IT LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970409

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19970409

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19970409

Ref country code: GB

Effective date: 19970409

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19970409

Ref country code: DK

Effective date: 19970409

Ref country code: AT

Effective date: 19970409

REF Corresponds to:

Ref document number: 151408

Country of ref document: AT

Date of ref document: 19970415

Kind code of ref document: T

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970501

REF Corresponds to:

Ref document number: 69218888

Country of ref document: DE

Date of ref document: 19970515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970710

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19970409

BERE Be: lapsed

Owner name: BAUDET PIERRE

Effective date: 19970531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

26N No opposition filed
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970531